Experimental Results to Design Lactic Acid for Carbonate Acidizing

Acidizing deep carbonate formations by Hydrochloric acid (HCl) is a complex task due to high reaction and corrosion rates. Mixing organic acids with HCl is a typical method to reduce the acid's reactivity and corrosivity. Lactic acid has not been investigated completely in the area of carbonate acidizing. Lactic acid has a dissociation constant similar to formic acid, which is approximately 10 times larger than acetic acid. Therefore, the objective of this work is to compare lactic/HCl blends with plain HCl and formic/HCl blends. Corrosion tests were conducted at high temperature on C-95 steel coupons to investigate associated corrosion damage. Coreflood tests were performed on Indiana limestone cores to mimic matrix acidizing treatment and to investigate amount of pore volumes required to breakthrough. All blends were prepared to be equivalent to 15 wt% (4.4 M) HCl for comparison. Lactic and formic acid concentrations were set to be (0.5 or 1 M), and HCl concentration was calculated as appropriate to reach a blend with strength of 4.4 M. In terms of corrosivity evaluation, blends of lactic and HCl acids showed a corrosion rate of up to 1.97 lb/ft2 at 300°F. The formic and HCl blend showed a corrosion rate of 1.68 lb/ft2 at the same temperature. The difference in corrosion rates between the two mixtures is due to molecular weight difference between lactic and formic acids. When both acids were prepared at 1 M, lactic acid blend required more HCl to be equivalent to 15 wt% HCl acid which was associated with an increase in corrosion rate. Coreflood results established acid efficiency curves for lactic/HCl acid blends. The curves highlighted the correlation between acid-core reactivity, injection rate, and dissolution pattern. Lactic/HCl blend was less reactive than formic/HCl mixture as the last required lower injection rate to obtain optimum pore volume to breakthrough at 300°F. Lactic/HCl blend was able to generate an optimum dissolution pattern as a dominant wormhole was shown on tested core plugs inlet face. This study expands the investigation of lactic acid utilization in carbonate acidizing. Major advantages rendered by using lactic acid with HCl include: (1) favorable dissolution pattern due to lactic acid being less reactive than HCl or formic acids, and (2) less corrosion rates comparing to HCl, that can reduce allocated costs for maintenance and replacements.

Evaluation of High Dissolving-Power Retarded Acid Recipes for Carbonate Acidizing

Development of retarded acid recipes that can have both adequate dissolving power and controllable reaction rate is desired to maximize the effectiveness of matrix stimulation treatments for oil and gas wells. Hydrochloric acid (HCl) has high dissolving power, however, the reaction rate with carbonate rock is uncontrollable and can cause face dissolution. Organic acids have low dissolving power and controllable reaction rate. The objective of this paper was to compare the effectiveness of three low viscosity retarded acid recipes with dissolving powers of 15 wt% and >20 wt% HCl equivalent. The examined acid recipes were 15/28 wt% emulsified acids, retarded acid recipes #1, #2 and #3, and 15/26 wt% HCl. The emulsified acids were at 30:70 ratio of diesel to acid. The retarded acid recipes were prepared at different dissolving power. Retarded acid recipe #3 was equivalent to 15 wt% HCl while retarded acid recipes #1 and #2 were equivalent to >20 wt% HCl. The calcite disc dissolution rate with retarded acids #1 and #2 was significantly lower than 26 wt% HCl and comparable to 15 wt% HCl at 75°F. The solubility of calcite discs in the retarded acid recipe #3 showed acid retardation higher than retarded acid recipes #1 and #2. The corrosion rate of retarded acid recipes #1 and #2 were 0.003-0.015 lb/ft2 at 250°F and 6 hrs, lower than both examined 26-28 wt% HCl and emulsified acids. The pitting indices of retarded acid recipes #1, #2, and #3 were 4, 2, and 1 respectively at 300°F. The pore volumes to breakthrough (PVBT) of retarded acid recipes #1 and #2 were slightly higher than retarded acid recipes #3 at 200°F. The PVBT values for 15 wt% and 28 wt% emulsified acid was comparable to retarded acid recipes #1, #2, and #3, confirming their retardation was effective.

The Role of CO2 in Carbonate Acidizing at the Field Scale – A Multi-Phase Perspective

Most lab-scale acidizing experiments are performed in core samples with 100% water saturation conditions and at pore pressures around 1100 psi. However, this is seldom the case on the field, where different saturation conditions exist with high temperature and pressure conditions. Carbon-di-Oxide (CO2), a by-product evolved during the acidizing process, is long thought to behave inertly during the acidizing process. Recent investigations reveal that the presence of CO2 dynamically changes the behavior of wormhole patterns and acid efficiency. A compositional simulation technique was adopted to understand the process thoroughly. A validated compositional numerical model capable of replicating acidizing experiments at the core-scale level, in fully aqueous environments described in published literature was utilized in this study. The numerical model was extended to a three-phase environment and applied at the field scale level to monitor and evaluate the impacts of evolved CO2 during the carbonate acidizing processes. Lessons learned from the lab-scale were tested at the field-scale scenario via a numerical model with radial coordinates. Contrary to popular belief, high pore pressures of 1,000 psi and above are not sufficient to keep all the evolved CO2 in solution. The presence of CO2 as a separate phase hinders acid efficiency. The reach or extent of the evolved CO2 is shown to exist only near the damage zone and seldom penetrates the reservoir matrix. Based on the field scale model's predictions, this study warrants conducting acidizing experiments at the laboratory level, at precisely similar pressure, temperature, and salinity conditions faced in the near-wellbore region, and urges the application of compositional modeling techniques to account for CO2 evolution, while studying and predicting matrix acidizing jobs.

Analytical Solutions of Carbonate Acidizing in Radial Flow

The flow of reactive fluids into porous media, a phenomenon known as reactive infiltration, is important in natural and engineered systems. While most of the studies in this area cover theoretical and experimental analyses in linear acid flow, the present work concentrates on radial flow conditions from a wellbore in the field and on finding exact analytical solutions to moving boundary problems of the uniform dissolution front. Closed-form solutions are obtained for the transient convection–diffusion which allow the demarcation of the range of applicability of the quasi-static limit. The fluid velocity dependency of the diffusion–dispersion coefficient is also examined by comparing results from analytical solutions from constant and velocity-dependent coefficients. These contributions form the basis for linear stability analyses to describe acid fingering encountered in reservoir stimulation.

Analytical Model for Estimation of Pore Volume to Breakthrough in Carbonate Acidizing with Organic and Mineral Acids

Acidizing is one of the most useful methods in the oil well stimulations. This treatment technique creates capillary wormholes in the carbonate formations to enhanced fluids flow production of a reservoir. One of the main indexes for recognizing the wormhole characterization is the pore volume to breakthrough number. Therefore, calculating this number is one of the main goals in the carbonate acidizing. Obtaining this number is always required for experimental works, which needs time, energy and cost. In this article, an empirical model was used to evaluate carbonate acidizing procedure in the limestone and dolomite cores as the carbonate cores. This empirical model measures the number of wormholes formed in the carbonate cores after acid injection by using the conservation of mass law. In this method, the transport relative reaction rates of acid and core inside the structure of wormhole was maintained during the wormhole creation process. Growing the wormhole in the carbonate formation was developed step by step. Changes in acid concentration as an injected fluid flow were accounted for in this empirical model. Also, the changes in carbonate porosity, the effect of Damköhler number, and injection rate were included in the model. Two types of carbonate rocks and five types of acids with different molar masses were used in this model for the analysis and validation of the model. The results from experimental works was significance and justifies the use of use of the law for mass transport and chemical reactions. Evaluation of the developed model with other experimental and numerical results gave an excellent assessment of 95.45% for the average accuracy and 0.9933 for the average coefficient of determination. Therefore, an empirical technique to approximate the pore volumes to breakthrough number in the limestone and dolomite cores with high accuracy using physical core and acid properties is proposed.

Effect of Isolated Fracture on the Carbonate Acidizing Process

Carbonate reservoirs are one of the most important fossil fuel sources, and the acidizing stimulation is a practical technique for improving the recovery of carbonate reservoirs. In this study, the improved two-scale continuum model, including the representative elementary volume (REV) scale model and the upscaling model, is used to study the acidizing process with an isolated fracture. Based on this model, a comprehensive discussion is presented to study the effect of the physical parameters of the isolated fracture on the acidizing results and dissolution images, including the isolated fracture geometry, location, and morphology. Results show that the isolated fracture system is still the target system for the acidizing stimulation. The isolated fracture provides a limited contribution to the core porosity. The permeability of the core sample with fracture can be obviously increased only when the fracture penetrates through the whole sample. The existence of the isolated fracture reduces the consumption of acid solution to achieve a breakthrough. The acidizing curve is sensitive to the change of the length, aperture, and position of the isolated fracture. The acidizing curve difference corresponding to different rotation angles has not changed significantly for clockwise rotation and anticlockwise rotation groups.

Flowback Analysis Methodologies and Precipitation Risk During Siderite-Bearing Carbonate Acidizing

Acidizing is the most commonly used method to stimulate carbonate reservoirs. To achieve a better assessment of the operation, a flowback analysis is conducted. Flowback analysis can give insights on the reservoir's response to the recipe. This analysis can be used to improve future treatment operations where some recommendations were deduced. The objective of this paper was to show the flowback analysis methodology following carbonate acidizing treatments with a focus on dissolved elements. X-ray diffraction (XRD), X-ray fluorescence (XRF), environmental scanning electron microscope (ESEM), and inductive coupled plasma (ICP) were used to determine the composition of flowback fluids and the filtered precipitate. Combining the data from different techniques onsite and in laboratory assess the development of a methodology for calculating more accurate amounts of dissolved elements, formation water, and volumes of recovered fluids. This analysis showed acid recipes efficiency of nearly 100% based dissolved calcite. Around 65% of injected fluids were lost into a formation. The iron concentration during the flowback was 1400 ppm, however, cumulative amount of iron in flow back samples was below expected value. Based on the formation's rock analysis, the theoretical amount of iron in the recovered flowback fluid was 1000 kg. The measured amount of iron was 500 kg and the rest could be assumed to be precipitated in a reservoir. This study helps in understanding the flowback fluid analysis and its importance by using a step-by-step analysis procedure for flowback fluid samples from the carbonate acidizing operations. The results of this study help in tracking the elements that potentially help in estimating the lost fluids volumes and percentage of success for a carbonate reservoir acid operation.